N-Oxide-Induced Ugi Reaction: A Rapid Access to Quinoline-C2-amino Amides via Deoxygenative C(sp2)-H Functionalization.

A logic-based replacement of the carboxylic acid component of the Ugi reaction by quinoline N-oxides has been developed. In this approach, the carboxylic isostere, quinoline N-oxide, plays a vital role by shifting the equilibria toward the product side with irreversible addition onto the C2-position of the N-oxide. Thus, aldehydes react with amines, isocyanides, and quinoline N-oxides to furnish quinoline four-component Ugi adducts. The unique reactivity of N-oxides with Ugi components opens an efficient synthetic route for the preparation of biologically active compounds.

Transition metal-free functionalization of 2-oxindoles via sequential aldol and reductive aldol reactions using rongalite as a C1 reagent.

A sequential one-pot classical aldol, transition-metal and hydride-free reductive aldol reaction is reported here for C(sp3)- H functionalization of 2-oxindoles using the multifaceted reagent rongalite. Here, rongalite functions as a hydride-free reducing agent and double C1 unit donor. This protocol enables the synthesis of a wide range of 3-methylindoline-2-ones and 3-(hydroxymethyl)-3-methylindolin-2-ones from 2-oxindoles (65-95% yields), which are the synthetic precursors for many natural products. Some of the important aspects of this synthetic approach include one-pot methylation and hydroxymethylation, low-cost rongalite (ca. $0.03 per 1 g), mild reaction conditions and applicability to gram-scale synthesis.